JP5237805B2 - Adhesives for non-ceramic flooring - Google Patents

Abstract

Non-ceramic floor coverings are bonded to a substrate by an aqueous adhesive that comprises a synthetic polymer as a binder and hydrolyzable silane groups.

Description

  The present invention relates to a method for bonding nonceramic floor coverings to a substrate, wherein an aqueous adhesive having a synthetic polymer as a binder is used, wherein the adhesive is hydrolyzed. It has a functional silane group. In particular, the invention relates to a method for joining a soft flooring such as carpet to a floor (substrate) or for joining a wood floor.

  The use of polymers with silane groups as adhesives for ceramic substrates, in particular for tiles, is described in EP-A-35332, EP-A-366969 and DE-A-19736409.

  Polymers having silane groups and for other applications are further e.g. from US 6,541,566, US 6,620,881, US 6,258,460, US 6,528,590 and US 5,240,992, and likewise EP-A-1,153,979, DE-A-19526759 and WO 99/37716.

  In the case of ceramic flooring, the interaction between the silane groups in the polymer and the ceramic substrate, in particular tile silicates, leads in particular to advantageous properties. In the case of non-ceramic substrates such as carpets and wood floors, no such interaction exists.

  High strength is desired in connection with bonding a wood floor or carpet to a substrate. Another important factor is high thermal stability: the bond should retain its strength even at relatively high temperatures caused by, for example, intense sun exposure.

  In the case of soft flooring, what is further desired is good so-called green strength development and open time. Good green strength formation means that an early and stable bond is formed after the carpet is laid on a substrate coated with an adhesive.

  Good open time means that a firm bond between the floor and the carpet is obtained even after the carpet has been aerated for a long time before being laid on the floor.

  Therefore, an adhesive for non-ceramic flooring that satisfies the above requirements with maximum effectiveness is desired.

  According to this desire, the method defined above has been found.

  The method involves the use of a synthetic polymer and an aqueous adhesive having hydrolyzable silane groups as a binder.

About Synthetic Polymers Above all, the polymer is in the form of an aqueous dispersion. Advantageously, the polymer or aqueous dispersion of the polymer is obtained by radical addition polymerization of ethylenically unsaturated compounds (monomers).

  The polymer comprises at least 40% by weight, more preferably at least 60% by weight and very particularly preferably at least 80% by weight, what is known as the main monomer.

  Main monomers are C1-C20 alkyl (meth) acrylates, vinyl esters of carboxylic acids having up to 20 carbon atoms, vinyl aromatic compounds having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, carbon atoms It is selected from vinyl ethers of alcohols having 1-10, aliphatic hydrocarbons having 2-8 carbon atoms and one or two double bonds, or mixtures of these monomers.

  Examples of alkyl (meth) acrylates include (meth) acrylic acid alkyl esters having C1-C10 alkyl groups such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.

  In particular, mixtures of (meth) acrylic acid alkyl esters are also suitable.

  Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate, versatic acid vinyl ester and vinyl acetate. Suitable vinyl aromatic compounds include vinyl toluene, α- and p-methyl styrene, α-butyl styrene, 4-n-butyl styrene, 4-n-decyl styrene and preferably styrene. Examples of nitriles are acrylonitrile and methacrylonitrile.

  Vinyl halides are ethylenically unsaturated compounds substituted by chlorine, fluorine, bromine, preferably vinyl chloride and vinylidene chloride.

  Examples of vinyl ethers include vinyl methyl ether or vinyl isobutyl ether. Preferred vinyl ethers are those of alcohols having 1 to 4 carbon atoms.

  As hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds, mention may be made of ethylene, propylene, butadiene, isoprene and chloroprene.

  Preferred main monomers are C1 to C20 alkyl acrylates and methacrylates, in particular C1 to C10 alkyl acrylates and methacrylates, and vinyl aromatic compounds, in particular styrene, and mixtures of alkyl (meth) acrylates and styrene.

  Very particular preference is given to methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, styrene and mixtures of these monomers.

  Particularly preferably, the polymer comprises at least 40%, in particular at least 60% and very particularly preferably at least 80% by weight of C1-C20, in particular C1-C10 alkyl (meth) acrylates.

  The polymer may have further monomers in addition to the main monomer, for example monomers containing carboxylic acid, sulfonic acid or phosphonic acid groups. Carboxylic acid groups are preferred. Examples that may be mentioned include acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.

  Further monomers are, for example, also monomers having hydroxyls, in particular C1-10 hydroxyalkyl (meth) acrylates and also (meth) acrylamides.

  Additional monomers that may be mentioned additionally include amino (meth) acrylates such as phenyloxyethyl glycol mono (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, and 2-aminoethyl (meth) acrylate.

  As further monomers, crosslinking monomers may also be mentioned.

  The polymer is, in one advantageous embodiment, produced by emulsion polymerization and therefore the product is an emulsion polymer.

  Alternatively, the production can be carried out by solution polymerization and subsequently dispersed in water.

  In the case of emulsion polymerization, ionic and / or nonionic emulsifiers and / or protective colloids and / or stabilizers are used as surface-active compounds.

  A detailed description of suitable protective colloids can be found in Houben-Weyl, Methoden der oraganischen Chemie, Volume XIV / 1, Makromolekulare Stoffe [macromolecular compounds], Georg-Thieme-Verlag, Stuttgart, 1961, pp.411. Seen at ~ 420. Suitable emulsifiers include anionic, cationic and nonionic emulsifiers. As an accompanying surface-active substance, it is advantageous to use exclusively emulsifiers whose molecular weight is different from that of protective colloids, usually below 2000 g / mol. When a mixture of surface-active substances is used, it will be appreciated that the individual components need to be compatible with each other and can be confirmed by several preliminary tests in case of any doubt. It is advantageous to use anionic and nonionic emulsifiers as surface-active substances. Conventional accompanying emulsifiers are, for example, ethoxylated fatty alcohols (EO units: 3-50, alkyl groups: C8-C36), ethoxylated mono-, di- and tri-alkylphenols (EO units: 3-50). , Alkyl groups: C4 to C9), alkali metal salts of dialkyl esters of sulfosuccinic acid and also alkyl sulfates (alkyl groups: C8 to C12), ethoxylated alkanols (EO units: 4 to 30, alkyl groups: C12). To C18), ethoxylated alkylphenols (EO units: 3 to 50, alkyl groups: C4 to C9), alkylsulfonic acids (alkyl groups: C12 to C18) and alkylarylsulfonic acids (alkyl groups: C9 to C9) C18) alkali metal salts and ammonium salts.

［式中、Ｒ^５およびＲ^６は、水素またはＣ４〜Ｃ１４アルキルであり、同時には水素でなく、かつＸおよびＹは、アルカリ金属イオンおよび／またはアンモニウムイオンであってよい］の化合物である。有利には、Ｒ^５およびＲ^６は、炭素原子６〜１８個、とりわけ炭素原子６、１２および１６個を有する線状または分岐状のアルキル基または水素であるが、しかしＲ^５およびＲ^６は、２つ同時には水素でない。有利には、ＸおよびＹは、ナトリウム、カリウムまたはアンモニウムイオンであり、ナトリウムがとりわけ有利である。とりわけ有利な化合物ＩＩは、ＸおよびＹがナトリウムであるものである。Ｒ^５は、炭素原子１２個を有する分岐状アルキル基であり、かつＲ^６は、水素またはＲ^５である。頻繁に、モノアルキル化された生成物５０質量％〜９０質量％の部分を含有する工業用混合物、例えばＤｏｗｆａｘ^（Ｒ）２ Ａ１（Dow Chemical Companyの商標）が用いられる。 Further suitable emulsifiers have the general formula

Wherein R ⁵ and R ⁶ are hydrogen or C 4 -C 14 alkyl, not simultaneously hydrogen, and X and Y may be alkali metal ions and / or ammonium ions. Advantageously, R ⁵ and R ⁶ are linear or branched alkyl groups or hydrogen having 6 to 18 carbon atoms, in particular 6, 12 and 16, but R ⁵ and R ⁶ are The two are not hydrogen at the same time. Advantageously, X and Y are sodium, potassium or ammonium ions, sodium being particularly preferred. Particularly preferred compounds II are those in which X and Y are sodium. R ⁵ is a branched alkyl group having 12 carbon atoms, and R ⁶ is hydrogen or R ⁵ . Frequently, technical mixtures containing monoalkylated portion of the product 50% to 90% by weight, for example ^Dowfax (R) (trademark of Dow Chemical Company) 2 A1 is used.

  Suitable emulsifiers can also be found in Houben-Weyl, Methoden der oraganischen Chemie, Volume 14/1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, pp.192-208.

Trade names of emulsifiers are, for example, Dowfax ^(R) 2 A1, Emulan ^(R) NP 50, Dextrol ^(R) OC 50, Emulgator 825, Emulgator 825 S, Emulan ^(R) OG, Texapon ^(R) NSO, Nekanil ^{(R ) ) 904 S, Lumiten (R)} I-RA, Lumiten E 3065, Disponil FES 77, Lutensol aT 18, a Steinapol VSL and Emulphor NPS 25.

  Usually surface active substances are used in amounts of 0.1% to 10% by weight, based on the monomers to be polymerized.

  Water-soluble initiators for emulsion polymerization are, for example, peroxodisulfuric acid, such as ammonium and alkali metal salts of sodium peroxodisulfate, hydrogen peroxide or organic peroxides, such as t-butyl hydroperoxide.

  Also suitable are those known as reduction-oxidation (redox) initiator systems.

  A redox initiator system consists of at least one reducing agent, usually an inorganic reducing agent, and one organic or inorganic oxidizing agent.

  The oxidizing component has, for example, the emulsion polymerization initiator already mentioned above.

The reducing component may be, for example, an alkali metal salt of sulfite, such as sodium sulfite, sodium bisulfite, an alkali metal salt of disulfite, such as a bisulfite addition compound having sodium disulfite, an aliphatic aldehyde and a ketone, such as acetone bisulfite. Or a reducing agent such as hydroxymethanesulfinic acid and its salts, or ascorbic acid. Redox initiator systems can be used with soluble metal compounds whose metal components can exist in multiple valence states.
Conventional redox initiator systems are, for example, ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, t-butyl hydroperoxide / sodium disulfite, t-butyl hydroperoxide / Na hydroxymethanesulfinate. The individual components, for example the reducing component, may be a mixture, for example a mixture of sodium salt of hydroxymethanesulfinic acid and sodium disulfite.

  The indicated compounds are mainly used in the form of aqueous solutions, where the lower concentration is determined by the amount of water that can be tolerated in the dispersion and the upper concentration is determined by the solubility of the respective compound in water. Is done. In general, the concentration is from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1.0 to 10% by weight, based on the solution.

  In general, the amount of initiator is 0.1% to 10% by weight, preferably 0.5% to 5% by weight, based on the monomers to be polymerized. It is also possible to use two or more different initiators in the emulsion polymerization.

  In the course of the polymerization, it is possible to use regulators, for example in amounts of 0 to 0.8 parts by weight per 100 parts by weight of monomers to be polymerized, and these regulators reduce the molar mass. Suitable examples include compounds having a thiol group, such as t-butyl mercaptan, ethyl thioglycolate acrylic ester, mercaptoethinol, mercaptopropyltrimethoxysilane or t-dodecyl mercaptan.

  The emulsion polymerization is generally carried out at 30 to 130 ° C, preferably 50 to 90 ° C. The polymerization medium may consist of water alone or otherwise consist of a mixture of water and a water miscible liquid such as methanol. It is advantageous to simply use water. Emulsion polymerization can be carried out as a batch operation or in the form of a feed process, for example a step process or a gradient process. Preference is given to a feeding method, in which a part of the polymerization batch is introduced as an initial charge, heated to the polymerization temperature and partially polymerized, and then the rest of the polymerization batch is mostly spatially The separated feed (one or more of which has the monomer in pure or emulsified form) is continuously fed stepwise into the polymerization zone or is subjected to a concentration gradient and added The polymerization is maintained throughout. In connection with the polymerization, it is also possible to include polymer seeds in the starting charge, for example for the purpose of setting improved particle sizes.

  It is known to those skilled in the art how to add an initiator to the polymerization vessel in the course of radical aqueous emulsion polymerization. It is either completely contained in the starting charge relative to the polymerization vessel or otherwise can be inserted continuously or stepwise at the rate at which it is consumed in the process of radical aqueous emulsion polymerization. . In particular, this depends on the chemistry of the initiator system and the polymerization temperature. Advantageously, a batch is included in the starting charge and the remainder is fed to the polymerization zone at a rate at which it is consumed.

In order to remove residual monomer, an initiator should usually be added even after the end of the actual emulsion polymerization, ie after at least 95% monomer conversion.
The individual components may be added to the reactor via the reactor bed from above, from the side or from below, in the case of feed processes.

  In the case of emulsion polymerization, an aqueous dispersion of a polymer having a solids content of generally 15% to 75% by weight, preferably 40% to 75% by weight, is obtained.

  For the purposes of the present invention, an advantageous solids content is 50% to 75% by weight, in particular 55% to 75% by weight.

  Due to the high space time yield of the reactor, preference is given to dispersions having a very high solids content. In order to be able to achieve a solids content> 60% by weight, a bimodal or polymodal particle size should be set. This is because otherwise the viscosity is too high and the dispersion can no longer be handled. Forming a new generation of particles can be achieved by adding seeds (EP81083), by adding an excess of emulsifier, or by adding a miniemulsion. A further advantage associated with the combination of low viscosity and high solid content is improved coating behavior at high solid content. One or more new generations of particles can be triggered at any time. Their formation is controlled by a particle size distribution aimed at low viscosity.

  The polymer thus produced is preferably used in the form of its aqueous dispersion.

  The viscosity of the polymer dispersion is preferably 50 to 1000 mPas, in particular 50 to 500 mPas.

  The glass transition point of the polymer or of the emulsion polymer is preferably from -60 ° C to 0 ° C, more preferably from -60 ° C to -10 ° C and very particularly preferably from -60 ° C to -20 ° C.

  The glass transition point can be measured by conventional methods such as differential thermal analysis or differential scanning calorimetry (see, eg, ASTM 3418/82, midpoint temperature).

  The pH value of the polymer dispersion is preferably 5-8, most preferably 5-7. In this range of pH, the hydrolysis reaction is inhibited, in particular inhibition is observed with alkoxy groups having more than 2 C atoms, in particular isopropoxy groups. Hydrolysis can occur or be promoted at a pH below or above this range or by increasing the temperature.

About Hydrolyzable Silane A hydrolyzable silane group is a molecular group that reacts with water (hydrolysis) to form an OH group bonded directly to a silicon atom.

  In particular, the hydrolyzable silane group has at least one alkoxy group bonded to a silicon atom.

  Hydrolyzable silane groups may be attached to the above synthetic polymer itself; alternatively, the adhesive may have additional additives with hydrolyzable silane groups.

［式中、Ｒ^１〜Ｒ^３は、互いに無関係に、それぞれ有機基であり、ただし、基Ｒ^１〜Ｒ^３の少なくとも１つは、アルコキシ基、とりわけＣ_１〜Ｃ_８アルコキシ基、有利にはＣ_１〜Ｃ_４アルコキシ基である］のものである。とりわけ有利には、基Ｒ^１〜Ｒ^３の２つ、３つまたは全ては、アルコキシ基である。 Silane groups attached to the polymer are notably of the formula I

Wherein R ^{1 to} R ³ are each independently an organic group, provided that at least one of the groups R ^{1 to} R ³ is an alkoxy group, especially a C _{1 to} C ₈ alkoxy group, preferably a C ₁ -C ₄ alkoxy radical is of. Particularly advantageously, two, three or all of the radicals R ^{1 to} R ³ are alkoxy radicals.

  Very suitable and suitable alkoxy groups are methoxy groups, ethoxy groups or else in particular isopropoxy groups.

The remaining groups are each independently an organic group, in particular organic groups which may have up to 20 carbon atoms and, if appropriate, heteroatoms such as O, N, S. Particularly suitable are alkyl groups, especially C ₁ -C ₂₀ , C ₁ -C ₁₀ alkyl groups.

  This silane group is bonded to the polymer via the 4-position free valence.

  Examples of suitable silane groups are mono-, di- or trialkoxysilane groups, the remaining groups being organic groups, especially alkyl groups.

  The polymer preferably has 0.001 to 0.1 mol, more preferably 0.001 to 0.01 mol and very particularly preferably 0.001 to 0.005 mol of silane groups per 100 g of polymer. .

  The silane group can be bound to the polymer as a result of copolymerization with a monomer having a silane group, use of a regulator having a silane group, or reaction of the polymer with a reactive compound having a silane group.

［式中、Ｒ^１〜Ｒ^３は、上で定義されたものと同じであり、かつＸは、少なくとも１つの、有利には１つの、共重合性の、エチレン性不飽和基、とりわけビニル基、殊にアクリル基またはメタクリル基、またはアリル基、または調節基(regulating group)（例えば鎖末端官能基化基(chain-terminating group)）、とりわけメルカプト基を有する有機基である］のものを包含する。共重合性基または調節基に加えて、とりわけＸは、例えば、共重合性基または調節基をケイ素原子に結び付ける、アルキレン基のようなスペーサー基を有することも可能である。しかしながら、共重合性基または調節基はまたケイ素原子に直接的に結合しうる。有利には、Ｘは、２００ｇ／モル未満の、とりわけ１００ｇ／モル未満の分子量を有する。 Suitable monomers or regulators having silane groups are of formula II

In which R ^{1 to} R ³ are the same as defined above and X is at least one, preferably one, copolymerizable, ethylenically unsaturated group, in particular a vinyl group , In particular acrylic or methacrylic groups, or allyl groups, or regulating groups (eg chain-terminating groups, especially organic groups having mercapto groups). To do. In addition to the copolymerizable group or modulating group, inter alia, X can also have a spacer group, such as an alkylene group, for example, that connects the copolymerizable group or controlling group to the silicon atom. However, the copolymerizable group or the control group can also be directly bonded to the silicon atom. Advantageously, X has a molecular weight of less than 200 g / mol, in particular less than 100 g / mol.

  Examples of monomers include vinyltriethoxysilane, vinyltriisopropoxysilane (wherein the vinyl group is directly bonded to the silicon atom), methacryloxypropyltrimethoxysilane (wherein the methacryl group is a spacer And is bonded to a silicon atom via a propyl group. As a regulator, mention may be made of mercaptopropyltrimethoxysilane.

  The amount of the above monomer or modifier in the polymer is selected such that the above silane group content is achieved; for this purpose, generally 0.005-5 parts by weight per 100 parts by weight of the polymer, more advantageous Is preferably from 0.01 to 2.0 parts by weight, most preferably from 0.1 to 1.0 parts by weight.

  Alternatively, the adhesive may have an additive having a hydrolyzable silane group. Advantageously, such an additive may be a compound having the group of formula I above. Preferred additives have a low molecular weight of 100 to 2000 g / mol, most preferably 100 to 1000 g / mol, in particular 100 to 250 g / mol. Most advantageously, such additives have the formula I above, wherein the free valence to the polymer is replaced by a further substituent R4.

R4 is a hydrogen atom or an organic group, especially an organic group which may have up to 20 carbon atoms and, if appropriate, heteroatoms such as O, N, S. Especially suitable are alkyl groups, especially _{C 1 ~C 20, C 1 ~C} 10 alkyl group or defined alkoxy groups above. Most preferred R4 is a hydroxy group, primary amino group, secondary amino group or tertiary amino group, isocyanate group, ureido group, carbamate group, anhydride group, carboxyl group or epoxy group such as glycidyl group. It has such a functional group. Particularly preferably, one, two or three groups of R ^{1 to} R ⁴ are alkoxy groups.

Examples of such additives are 3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane. Suitable silanes are offered under the trade name Geniosil ^(R) from Wacker.

  The adhesive may have a synthetic polymer having a silane group or an additive having a silane group, or may have both a synthetic polymer having a silane group and an additive having a silane group.

  The total amount of silane groups (corresponding to formula I) is preferably 0.001 to 0.1 mol, more preferably 0.001 to 0.01 mol and very particularly preferably 0, per 100 g of synthetic polymer. 0.001 to 0.005 moles, where the silane group may be attached to the polymer or may be an additive or two parts.

About Use of Aqueous Adhesive Aqueous adhesive has the above polymer as a binder. An aqueous adhesive consists solely of a binder or an aqueous dispersion of a binder; alternatively it may have additional components.

  Water-based adhesives are used for non-ceramic flooring according to the present invention. Ceramic flooring is in particular tiles.

  In the case of non-ceramic flooring, a distinction should be made between soft flooring and non-soft flooring.

For use in soft flooring For this application, water-based adhesives include inter alia fillers, tackifying resins (tackifiers), thickeners, foam suppressors or wetting agents as further additives. A dispersion aid may be included.

  For this application, the adhesive preferably has a filler.

  Suitable fillers include inter alia inorganic fillers. Examples that may be mentioned include finely ground chalk or precipitated chalk, in particular those having an average particle size generally between 2 and 50 mm and / or quartz powder having a normal average particle size of 3 to 50 mm .

  The amount of filler is in particular 10 to 1000 parts by weight, more preferably at least 30 parts by weight, most preferably at least 60 parts by weight per 100 parts by weight of polymer (solid, without solvent).

  Preferred tackifying resins (tackifiers) are abietic acid or modified abietic acid, such as hydrogenated abietic acid or disproportionated abietic acid, having a glass transition point of 0-90 ° C., preferably 40-85 ° C. Resins based on acids or esters of these compounds.

  This type of resin is particularly known as rosin.

  For improved surface wettability, the adhesive should have inter alia wetting aids such as fatty alcohol ethoxylates, alkylphenol ethoxylates, sulfosuccinates, nonylphenol ethoxylates, polyoxyethylene / propylene or sodium dodecyl sulfonate. Is possible.

  For example, per 100 parts by weight of the polymer (solid, without solvent) in the aqueous adhesive, the wetting agent is 0 to 5 parts by weight, the thickener is 0 to 10 parts by weight, and the preservative is 0 to 3 parts. The amount of the foam inhibitor may be included in an amount of 0 to 10 parts by mass.

  The adhesive is advantageously essentially free of, and more preferably completely free of, for example, organic solvents and plasticizers such as butyl acetate, toluene or phthalate. Therefore, it is more advantageous for organic compounds having a boiling point below 300 ° C. under atmospheric pressure (1 bar), preferably in an amount of less than 0.5 parts by weight per 100 parts by weight of polymer (solid, no solvent). Is contained in an amount of less than 0.1 parts by mass, very advantageously in an amount of less than 0.05 parts by mass and especially in an amount of less than 0.01 parts by mass. Particularly advantageously, the adhesive fulfills the requirements free from the emissions defined by the German Association for Emissions-Controlled Installation Materials (Gemeinschaft Emissionskontrollierter Verlegewerkstoffe).

The amount of emissions is measured by the chamber test method. The floor adhesive or composition of the present invention is applied at 300 g / m ² to a glass plate whose size is controlled by the volume of the chamber. The chamber is loaded with 0.4 m ^{2 of} coated glass plate per 1 m ^{3 of} chamber volume. Dissipation conditions in a stainless steel test chamber (whose volume is at least 125 liters) are 23 ° C., 50% relative humidity, and a timed ventilation system that provides full ventilation every two hours. For this purpose, a defined volume of airflow is conducted to the adsorbent. Subsequent desorption is performed and the released material is measured by gas chromatography (GC-MS coupling) or liquid chromatography. Long-term emissions are measured in mg / m ³ using toluene as a standard. Dissipated material whose chamber concentration is greater than 20 mg / m ³ is identified and calibrated with the identified pure material. Dissipated material whose chamber concentration is less than 20 mg / m ³ is not individually identified. In these cases, toluene is used for calibration.

  All substance values are added.

In the case of the composition according to the invention, the total emission value of all organic compounds is advantageously not more than 1500 mg / m ³ and in particular not more than 500 mg / m ³ .

  Aqueous adhesives can easily be prepared, for example, by adding fillers and, if appropriate, further additives, to the aqueous polymer dispersion resulting from emulsion polymerization, with stirring.

  The water content of the aqueous adhesive can be, for example, 5% to 50% by weight, in particular 10% to 40% by weight, based on the aqueous composition as a whole.

  Flexible flooring materials are, for example, PVC (in the form of a multilayer or homogeneous material), foams with fiber backing (eg jute), polyester nonwovens, rubber materials, textiles, eg various backings (eg polyurethane foam) , Styrene-butadiene foam, fiber secondary backing), carpet or other flooring made of needle felt material, polyolefin material or linoleum material.

  These soft flooring materials can be bonded to substrates such as wood, plastic, screeding, concrete, mineral substrates such as ceramic tiles, metal substrates and the like.

  The adhesive can be applied to the substrate using, for example, a toothed applicator. After customary ventilation, flooring is laid.

For use for non-soft flooring Non-soft flooring for the present invention is in particular wood floors, preferably wood block floors or laminate floors. In this case, according to the present invention, the adhesive is not used to bond the individual plates together but rather is used to bond the plates to the substrate (non-floating installation).

  The aqueous adhesive has the above polymer as a binder. For this application, the aqueous adhesive may simply consist of a binder or an aqueous dispersion of the binder; alternatively it may comprise further components, notably fillers, tackifying resins (tackifiers), among others. , Thickeners, foam inhibitors or wetting agents and / or dispersion aids.

  The adhesive composition of the present invention has a good level of performance characteristics such as peel strength (adhesion), very good shear strength (cohesive strength in the adhesion layer), green strength formation (early shear strength formation). , Open time (still good adhesion even after prolonged ventilation) and heat resistance.

A) Example of non-soft flooring (wood floor)
Polymer synthesis General data: The reaction was carried out as a semi-batch emulsion polymerization in a reactor equipped with a mechanical stirrer. The following materials were used in the polymerization: SULFOLE ^™ 120 t-dodecyl mercaptan (from Phillips Petroleum of Bartlesville, Oklahoma) as a chain transfer agent, Trilon BX, TEXAPON ^™ K 12 PA 15 sodium lauryl sulfate as a 15% aqueous solution (From Cognis Corp., Cincinnati, Ohio) and Iconol ^™ TDA-8 ethoxylated nonionic surfactant (BASF Corp.) as a 90% solution were used as surfactants; as silanes from Degussa DYNASYLAN VTEO (= vinyltriethoxysilane) and COATOSIL 1706 (= vinyltris (isopropoxy) silane) from GE Silicones were used.

  Method outlined here for Latex 1: 199.6 g of water, 0.06 g of 40% aqueous solution of Trilon BX g and 0.6 g of ascorbic acid were charged to the reaction vessel and the mixture was heated to 90 ° C. . 10% was transferred from the initiator feed of 116.2 g water and 8.7 g sodium persulfate and added to the reaction mixture. Subsequently, the following three separated feeds were added in this manner at a constant feed rate: (a) the remainder of the initiator feed was added within 3.75 hours; (b) monomer emulsion mixed feed (165.0 g of water, 45.2 g of 15% aqueous sodium lauryl sulfate solution, 5.0 g of 90% aqueous Iconol TDA-8, 45.2 g of 10% sodium hydroxide solution, 1.1 g of t-dodecyl mercaptan, methacrylic acid 20 g from 33.9 g and consisting of 1039.6 g of n-butyl acrylate) was added within 15 minutes, followed by another 60 g within 15 minutes and the remainder within 3.0 hours; (c) After a time delay of 30 minutes, 56.5 g of acrylonitrile was added within 2.5 hours. The temperature was maintained at 90 ° C. throughout the entire duration of the feed. After the feeding phase, the monomer emulsion tank was flushed with 16.3 g of water and the temperature was changed to 85 ° C. The dispersion was post-striped by adding the following two mixtures as two separate feeds over the course of 2 hours: (a) 6.5 g of 70% t-butyl hydroperoxide solution and 33. water. 5 g and (b) sodium metabisulfite 4.5 g, acetone 2.6 g and water 32.9 g. Next, a solution of 22.6 g of 10% NaOH and 19.2 g of water was added, and 1.5 g of 12.5% hydrogen peroxide was added. The latex was then cooled and optionally post-additives (insecticides).

Latex 2: Preparation of Latex 1, with these changes: 11.3 g AAEM and 1028.3 g n-butyl acrylate were used.
Latex 3: Preparation of Latex 1, with these changes: 6.8 g vinyltriethoxysilane, 1028.3 g n-butyl acrylate and 61.0 g acrylonitrile were used.
Latex 4: Preparation of Latex 1, with these changes: 8.5 g vinyltris (isopropoxy) silane, 1028.3 g n-butyl acrylate and 59.3 g acrylonitrile were used.
Latex 5: 156.0 g of water in the starting charge and 98.4 g of water in the monomer emulsion were used.
Latex 6: Preparation of Latex 1, with these changes: 4.2 g vinyltriethoxysilane, 1100.0 g n-butyl acrylate, 156.0 g water in the starting charge and water 94 in the monomer emulsion .8 g was used.
Latex 7: Preparation of Latex 1, with these changes: 22.6 g of diacetone acrylamide and 1017.0 g of n-butyl acrylate were used.
Latex 8: Preparation of Latex 1, with these changes: 4.5 g vinyltris (isopropoxy) silane, 1032.3 g n-butyl acrylate and 59.3 g acrylonitrile were used.
Latex 9: Preparation of Latex 1, with these changes: The starting charge was 195.0 g water, 0.07 g Trilon BX and 0.65 g ascorbic acid; the monomer emulsion mixture was 144.3 g water, 52.0 g of 15% aqueous sodium lauryl sulfate solution, 5.8 g of 90% aqueous Iconol TDA-8, 52.0 g of 10% aqueous sodium hydroxide solution, 9.8 g of 53% aqueous acrylamide solution, 19.5 g of methacrylic acid, and 1171.3 g of n-butyl acrylate; the other ingredients were the same as in Latex 1 multiplied by a factor of 1.08.
Latex 10: Preparation of Latex 9, with these changes: 9.8 g vinyltris (isopropoxy) silane and 1161.6 g n-butyl acrylate were used.
Latex 11: Preparation of Latex 9, with these changes: 169.0 g of water in the starting charge and 98.0 g of water in the monomer emulsion were used.
Latex 12: Preparation of Latex 9, with these changes: 7.2 g vinyltris (isopropoxy) silane and 1164.2 g n-butyl acrylate were used.
Latex 13: Preparation of latex 9, styrene is used instead of acrylonitrile.
Latex 14: Preparation of Latex 9, with these changes: 65.0 g styrene and 39.0 g acrylonitrile were used.
Latex 15: Preparation of Latex 9, with these changes: 39.0 g styrene and 65.0 g acrylonitrile were used.
Latex 16: Preparation of Latex 9, with these changes: 26.0 g of methacrylic acid and no acrylamide.
Latex 17: Preparation of Latex 9, with these changes: 7.2 g vinyltris (isopropoxy) silane, 1164.2 g n-butyl acrylate and 0.7 g t-dodecyl mercaptan were used.
Latex 18: Preparation of Latex 9, with these changes: 84.5 g styrene and 19.5 g acrylonitrile were used.

Measurement of total solids, pH, particle size, and viscosity. Total solids content was measured by use of a CEM Labware 9000 Microwave Moisture / Solids Analyzer instrument with a power setting of 70%. The pH measurement was performed by using an Orion 310 pH meter, in which case calibration was performed before use. Particle size was achieved by use of a NICOMP ^™ 308 Submicron Particle Sizer utilizing dynamic light scattering at 25 ° C. and 90 ° angle. The viscosity of each latex sample was obtained using a Brookfield RV BF-1 DVII viscometer.

Latex 1: solid content 62.8%, pH 7.3, viscosity 290 cps
Latex 2: Solid content 63.8%, pH 7.3, viscosity 290 cps
Latex 3: Solid content 63.4%, pH 6.6, viscosity 270 cps
Latex 4: Solid content 63.2%, pH 6.4, viscosity 360 cps
Latex 5: solid content 67.7%, pH 6.4, viscosity 1320 cps
Latex 6: solid content 67.5%, pH 6.4, viscosity 280 cps
Latex 7: solid content 62.6%, pH 6.5, viscosity 70 cps
Latex 8: solid content 63.2%, pH 6.4, viscosity 70 cps
Latex 9: solid content 65.7%, pH 7.6, viscosity 420 cps
Latex 10: solid content 67.1%, pH 7.6, viscosity 560 cps
Latex 11: solid content 68.7%, pH 7.4, viscosity 900 cps
Latex 12: solid content 67.0%, pH 7.8, viscosity 460 cps
Latex 13: solid content 65.5%, pH 7.0, viscosity 1000 cps
Latex 14: solid content 66.0%, pH 7.8, viscosity 490 cps
Latex 15: solid content 66.1%, pH 8.1, viscosity 640 cps
Latex 16: solid content 67.3%, pH 7.0, viscosity 400 cps
Latex 17: solid content 66.8%, pH 8.3, viscosity 430 cps
Latex 18: solids content 67.0%, pH 7.6, viscosity 594 cps
Viscosity at pH 9.5: Latex 1-520 cps, Latex 2-340 cps,
Latex 3-270 cps, Latex 4-340 cps, Latex 5-> 10000 cps, Latex 6-> 10000 cps, Latex 7-130 cps, Latex 8-141 cps, Latex 9-187 cps, Latex 10-270 cps, Latex 11-986 cps, Latex 12- 482 cps, Latex 13-> 10000 cps, Latex 14-594 cps, Latex 15-574 cps, Latex 16-478 cps, Latex 17-424 cps, Latex 18-1536 cps.

Latex film preparation, mechanical properties (tensile test) and water absorption. A latex film was first prepared by adding sufficient water to achieve a total solids content of 40%. The resulting diluted dispersion was then poured into a Teflon mold and air dried at 25 ° C. for 3 days at 50% humidity. Optionally, the film was then placed in an oven at 50 ° C. for a specified time. The film thickness was about 0.02 inches.
Sample preparation for tensile experiments was performed by first placing release paper on both sides of the sample and cutting the corresponding 0.158 "(with respect to width)" dog bone "type sample. Instron 4505 equipped with a 22 Ib load cell was used, elongation was performed at 7.9 inches / minute, and maximum strength and elongation at break were recorded (see Table 1).

  The water absorption of the film was determined by cutting a 2 inch × 2 inch film piece, measuring the dry mass, immersing the piece in deionized water at room temperature for 24 hours, and removing them from the water. Was determined by measuring the mass. The water absorption is the mass percentage obtained, and it consists of an average of 3 to 5 specimens per test sample.

Curing condition 1: 5 days at room temperature Curing condition 2: 5 days at room temperature and 1 day at 50 ° C. Curing condition 3: 5 days at room temperature and 2 days at 50 ° C. Curing condition 4: 5 days at room temperature and 3 days at 50 ° C. Curing condition 5: 5 days at room temperature and 9 days at 50 ° C. Water absorption under curing condition 2;
Latex 1-29.2%
Latex 3-25.0%
Latex 4-31.3%
The latex pH was adjusted to the following value with 30% aqueous sodium hydroxide and then curing condition 2 was applied (maximum strength at N / mm2; elongation at break in%)

For the shear test, the sample was formulated as follows: While stirring, the following ingredients were added to 126 g of aqueous dispersion (solid content 60-65%): 0.75 g of Drewplus L-108 (Ashland Chemicals) ), 0.15 g of Igepal CO 530 (from Rhodia), 1.5 g of an aqueous slurry of 20% STPP (= sodium tripolyphosphate, from Astaris). To this mixture, 135 g of Duramite (from Imerys) was slowly added under strong stirring. The pH was adjusted to 8-9 using aqueous KOH and finally 3.0 g of Latecoll D (BASF Aktiengesellschaft) was added.
Wood-on-wood shear results were obtained using a slightly modified ASTM D 3498 protocol. All dimensions for hardwood and plywood were used as defined in the aforementioned standards. However, after placing two beads of adhesive on hardwood in a caulking machine, the adhesive was air dried for 10 minutes before placing the plywood strip. A 10 pound weight was then used to press the plywood onto the hardwood. A nail was then used to secure the plywood strip. The test was then performed as specified after air drying for 24 hours, 5 days, and 2 weeks at 25 ° C. at 50% humidity. Compression was performed with an Instron 4504 at a crosshead speed of 0.2 inches / minute and the maximum load was recorded.

Shear test. Samples were cured under CT & H conditions. Numbers refer to stress at maximum value (N / mm2)

  Latex 10 Polymer film Tensile rate: cure condition 1 yielding 0.66 N / mm 2 and 2165%; effect condition yielding 1.4 and 1330%; cure condition 3 showing 1.87 and 1412%.

The pH of the latex was adjusted to the following value with 30% aqueous sodium hydroxide solution and then curing condition 2 was applied (maximum strength at N / mm2; elongation at break in%, water absorption in%)

90 degree peel test (in N / mm2)

  Curing condition 2 was applied for these film tests.

  Latex 16 tensile and elongation data according to cure condition 2; 0.78 and 2390%. Data after addition of 0.15% calcium hydroxide: 1.60 and 1684%; after addition of 0.30% calcium hydroxide: 2.38 and 948% elongation.

  Latex 17 and 18 tensile and elongation data using cure condition 2: Latex 17 shows 1.22 and 1538% elongation. Latex 18 exhibits 1.22 and 2111% elongation.

Abbreviations used in the following table:
MAA: Methacrylic acid AM. Acrylamide BA: n-butyl acrylate silane 1: Vinyl triethoxysilane silane 2: Vinyl (tri-isopropoxy) silane DAAM: Diacetone acrylamide AAEM: Acetoacetylethyl methacrylate Sty: Styrene ACN: Acrylonitrile

B) Examples for soft flooring Preparation of polymer dispersion by emulsion polymerization For emulsion polymerization, polystyrene seeds (1.5% by weight with respect to the monomer) and a third of itaconic acid were included in the starting charge.

The polymerization temperature was 78 ° C. Initiator used was sodium persulfate was emulsifier used was Texapon ^R NSO-IS (aliphatic, ethoxylated Na salt).

  Monomer was metered in over 5.5 hours and initiator solution was metered in over 6 hours.

  The composition of the polymer is indicated in the table below (in parts by weight).

Aqueous Composition Preparation The polymer dispersion was mixed with fillers, tackifiers and further additives as noted in the table below.

Amount in parts by mass

3. Performance Test - the green strength adhesive, using a DIN coater, detached orientation with cement fiberboard panel ^{(e.g., Eternit} (R) 2000) was discharged (20 × 50 cm). The applied amount is about 350 to 400 g / m ² . Needle felt flooring strips (NFC strips) are placed on the adhesive layer after 10 minutes and pressed by rolling a 2.5 kg roller back and forth three times. Thirty minutes later, the peel resistance is measured at N / 5 cm by pulling the strip with a picker.

-Heat resistance After exposure to air for 5 minutes, 5 PVC test strips (60 x 50 mm) coated with adhesive adhere to the fiber cement defined in DIN 16860 (10 cm2 adhesive surface) and 14 Maintained in standard laboratory atmosphere for days. They are then adjusted to 50 ° C. for 30 minutes, then a 2 kg load is applied and the specimens are kept at 50 ° C. in a circulating air furnace for 8 to a maximum of 1440 minutes until they are pulled apart.

The results are shown in the following table:

Claims (19)

A method of joining a non-ceramic flooring to a substrate, wherein a water-based adhesive having a polymer comprising at least 40% by mass of a C1-C20 alkyl (meth) acrylate as a binder is used, and the adhesive is a hydrolyzable silane A method of joining a non-ceramic flooring having a base to a substrate.   The method of claim 1, wherein the polymer itself has hydrolyzable silane groups or the adhesive has a further additive having hydrolyzable silane groups. A silane group is attached to the polymer, and the silane group has the formula

The method according to claim 1 or 2, wherein each of R ^{1 to} R ³ is an organic group independently of each other, provided that at least one of the groups is an alkoxy group.   The method according to any one of claims 1 to 3, wherein the amount of silane groups is 0.001 to 0.1 mol / 100 g polymer. Silane groups, copolymerization with a monomer having a silane group, the use of modulating agents having a silane group or a polymer, attached to the polymer as a result of reaction with a reactive compound having a silane group, claim 1 4 The method according to any one of the above. The method according to any one of claims 1 to 5 , wherein the mass fraction of the regulator and monomer having a silane group is 0.005 to 5 parts by mass per 100 parts by mass of the polymer. 7. A process according to any one of claims 1 to 6 , wherein the polymer is an emulsion polymer and is in the form of an aqueous polymer dispersion. The method according to any one of claims 1 to 7 , wherein the solid content of the aqueous polymer dispersion is 50% by mass to 75% by mass. The method according to claim 8 , wherein the solid content of the aqueous polymer dispersion is 55% by mass to 70% by mass. The method according to any one of claims 1 to 9 , wherein the viscosity of the polymer dispersion is 50 to 1000 mPas. The method according to claim 10 , wherein the viscosity of the polymer dispersion is 50 to 500 mPas. The method according to any one of claims 1 to 11 , wherein the glass transition point of the polymer is -60 to 0 ° C. 13. A method according to any one of claims 1 to 12 for joining soft flooring. 14. The method of claim 13 , wherein the soft flooring is carpet. 14. The method of claim 13 , wherein the adhesive has 10 to 400 parts by weight filler per 100 parts by weight polymer (solid). The method according to any one of claims 13 to 15 , wherein the adhesive may further comprise a tackifying resin, a thickener and a wetting agent. The method according to any one of claims 13 to 16 , wherein the adhesive is applied to the substrate and the flooring is subsequently laid. 13. A method according to any one of claims 1 to 12 , for joining non-soft floors made of wood. The method of claim 18 , wherein the wood is a wood block or laminate.